CN107986248B - Preparation method of bis (fluorosulfonyl) imide - Google Patents
Preparation method of bis (fluorosulfonyl) imide Download PDFInfo
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- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 21
- 238000004821 distillation Methods 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims 2
- 238000007789 sealing Methods 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 abstract description 11
- 150000007530 organic bases Chemical class 0.000 abstract description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 150000001447 alkali salts Chemical class 0.000 abstract description 4
- 238000006073 displacement reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000012025 fluorinating agent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910006095 SO2F Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- -1 Polytetrafluoroethylene Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PPFAPKNCEXDZNN-UHFFFAOYSA-N N=[SH2].F.F Chemical compound N=[SH2].F.F PPFAPKNCEXDZNN-UHFFFAOYSA-N 0.000 description 2
- 229910003844 NSO2 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910005948 SO2Cl Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- 229910005185 FSO3H Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a preparation method of bis (fluorosulfonyl) imide, which comprises the steps of reacting sulfuryl fluoride with ammonium fluoride and triethylamine to prepare an organic alkali salt of bis (fluorosulfonyl) imide, carrying out a displacement reaction on the organic alkali salt and a strong acid, and carrying out reduced pressure distillation to obtain high-purity bis (fluorosulfonyl) imide. The method of the invention uses SO2F2、NH4F and organic base are used as raw materials, and the use of strong corrosive FSO is avoided3H is taken as a raw material; the process is simple, the continuous operability is strong, the product is easy to separate and purify, high-purity (more than or equal to 99 percent) HFSI can be prepared by reduced pressure distillation, and the yield can reach more than 90 percent; no chloride ion participates in the whole reaction, and the product quality is stable.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrolytes, and particularly relates to a preparation method of bis (fluorosulfonyl) imide.
Background
Bis-fluorosulfonylimide (CAS:14984-73-7) of formula (SO)2F)2NH, HFSI for short, density 1.892g/cm3The melting point is 17 ℃ and the boiling point is 170 ℃. HFSI and its salt are widely used in acid catalyst, ionic liquid, selective fluorinating agent and other fields, wherein HFSI is used for preparing lithium bis (fluorosulfonyl) imide (LiN (SO) in chemical formula)2F)2LiFSI) has the characteristics of proper conductivity, high thermal stability, high electrochemical stability, low probability of side reaction and the like, is an electrolyte substance with wide application prospect, and has important industrial application value in the fields of lithium ion batteries, ionic liquid catalysts, super capacitors and the like.
The preparation method of HFSI mainly comprises the following steps:
US4315935, CN102786452, m.berran et al, z.anorg.allg.chem.2005,631,55, r.appel et al,1962,95,1753 and the like disclose chlorosulfonic acid (FSO)3H) Thionyl chloride (SOCl)2) And sulfamic acid (NH)2SO3H) Firstly, the bischlorosulfonimide ((SO) is synthesized2Cl)2NH)，(SO2Cl)2And fluorinating NH by a fluorinating agent and lithiating a lithium-containing substance to prepare LiFSI. The method has the advantages of easily obtained raw materials, lower cost and mild reaction conditions, but the method has long process flow, and chloride ions introduced in the synthesis process are difficult to effectively remove, thereby seriously influencing the industrial application of LiFSI. (SO)2Cl)2The preparation of HFSI from NH mainly consists in the selection of fluorinating agents, among which M.Berran et al, Z.Anorg.Allg.Chem.2005,631,55, using KF as fluorinating agent, and (SO)2Cl)2NH prepares potassium bis (fluorosulfonyl) imide (KFSI) in one step, but reactants are solid and no solvent is added, which influences mass transfer efficiency. Krumm et al, Inorg. chem.1998,37,6295 used SbF3As fluorinating agent, but due to the reaction by-product SbCl3Since HFSI is easily sublimed and distilled out together with the main product HFSI during vacuum distillation, it is very difficult to purify HFSI by vacuum distillation, it is difficult to obtain HFSI with a purity of more than 99.5%, and the yield is as low as about 45%. By NH2SO3H is first synthesized to (SO)2Cl)2NH, and then fluorinated by a fluorinating agent to prepare HFSI, wherein MFn is the fluorinating agent.
NH2SO3H+2SOCl2+ClSO3H→(SO2Cl)2NH+2SO2+3HCl (1)
U.S. Pat. Nos. 8337797, 9156692, 5916475, Inorg. Synth.11,138-43(1968) and others disclose urea (CO (NH)2)2) With fluorosulfonic acid (FSO)3H) Process for preparing HFSI by mixed heating reaction, HFSI formed therefrom andexcess addition of FSO3H can be recovered by distillation under reduced pressure. Wherein US8337797 discloses a Polytetrafluoroethylene (PTFE) material reactor, the reaction temperature is 120-130 ℃, and the urea-based yield of the HFSI product is about 40%. FSO used in the method3H is expensive, the equipment is extremely corrosive, and the method has low yield, so that the cost is very high.
3FSO3H+CO(NH2)2→(SO2F)2NH+NH4HSO4+HF+CO2 (3)
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of bis (fluorosulfonyl) imide, which is simple to operate, high in purity and yield of the prepared product and free of chloride ions.
The purpose of the invention is realized by the following technical scheme:
a method for preparing bis (fluorosulfonyl) imide, comprising: sulfuryl fluoride (SO)2F2) And ammonium fluoride (NH)4F) Reacting in the presence of organic base to produce organic base salt of difluoride sulfimide (HFSI), rotary distilling to remove solvent and unreacted organic base, adding strong acid to replace HFSI from organic base salt of difluoride sulfimide, and vacuum distilling to obtain high-purity HFSI.
2SO2F2+NH4F+4Et3N→[(SO2F)2N]H·Et3N+3Et3N.HF (4)
2[(SO2F)2N]H·Et3N+H2SO4→2(SO2F)2NH+(Et3N)2.H2SO4 (5)
The preparation method of the bis (fluorosulfonyl) imide provided by the invention comprises the following specific steps:
(1) reacting NH4F. Mixing organic base and organic solvent, placing in a high pressure reaction kettle, introducing SO at 0-80 deg.C and 0-1.5Mpa (gauge pressure)2F2Carrying out fluorination reaction for 10-36 hours to obtainA reaction solution containing an organic alkali salt of bis (fluorosulfonyl) imide and an organic alkali salt of HF;
(2) and (2) removing the solvent and the unreacted organic base from the reaction solution obtained in the step (1) by rotary evaporation, adding strong acid to replace the HFSI, and preparing the high-purity HFSI by reduced pressure distillation.
In the step (1), the organic base is selected from one or more of triethylamine, pyridine, 4-Dimethylaminopyridine (DMAP), triethylene diamine and tetramethylpropylene diamine (TMPDA), preferably one or more of triethylamine, pyridine and TMPDA, and most preferably triethylamine.
The organic solvent is one or more of acetonitrile, ethyl acetate, N-methyl-2-pyrrolidone (NMP), benzene and toluene, preferably one or more of acetonitrile, NMP and ethyl acetate, most preferably acetonitrile, and because the acetonitrile is dissolved in water and the salt generated in the product is also dissolved in water, the solvent cannot be removed by an extraction method, and the solvent is generally removed by a rotary evaporation method. The rotary evaporation temperature is controlled at 50-100 ℃, preferably 80 ℃, the pressure is-0.08 MPa (gauge pressure), the temperature is too low, acetonitrile and excessive triethylamine can not be completely removed by rotary evaporation, and the temperature is too high, so that other products are volatilized, and the yield is influenced.
The molar ratio of the sulfuryl fluoride to the ammonium fluoride to the organic base is 2-4:1:1-6, preferably 2.4-3.5:1: 4-6. The organic base is used as an acid-binding agent and is mainly used for combining with HF and HFSI generated in the reaction.
In the technical scheme of the invention, ammonium fluoride is insoluble in an organic solvent and exists in a reaction system in a solid mode; and introducing sulfuryl fluoride into the mixed solution of ammonium fluoride, organic amine and an organic solvent. The sulfuryl fluoride gas has certain solubility in the organic solvent, when the pressure is lower than the gauge pressure by 0MPa, the fluoridation reaction is started after the gauge pressure is increased to 0MPa due to the small amount of the sulfuryl fluoride introduced, low concentration and slow reaction rate; decomposition of ammonium fluoride to NH3The reaction with sulfuryl fluoride, the reaction time depends on the decomposition rate of ammonium fluoride, the reaction temperature and the pressure of sulfuryl fluoride are increased, the local concentration is too high, and the generated by-product H2NSO2NH2The content is increased. By NH4F replacing NH3Only one gas needs to be introducedSimple and convenient operation and can effectively avoid NH3Local over-high concentration, and reduced generation of byproduct H by reaction with sulfuryl fluoride2NSO2NH2。
Preferably, the fluorination reaction temperature is 5-50 ℃, the reaction pressure is 0.1-0.8MPa (gauge pressure), and the reaction time is 12-24 hours.
In the step (2), the strong acid is one or more of concentrated sulfuric acid (98 mass%), concentrated hydrochloric acid (37 mass%), concentrated nitric acid (65 mass%), hydriodic acid (57 mass%), hydrobromic acid (47 mass%), and perchloric acid (70 mass%), preferably one or more of concentrated sulfuric acid, perchloric acid, and concentrated nitric acid, and most preferably concentrated sulfuric acid. The concentrated sulfuric acid is in excess in the system, and the molar ratio of sulfuric acid to ammonium fluoride is generally controlled to be at least 1:1, preferably 1.02 to 1.5: 1.
The pressure of the reduced pressure distillation is 650Pa, and HFSI is collected at 85 ℃/650 Pa. Due to the difference in acidity, concentrated sulfuric acid can displace only HFSI from its organic base, and the triethylamine salt of HF remains in the distillation mother liquor.
Compared with the existing preparation method, the invention has the following advantages:
the method of the invention uses SO2F2、NH4F and organic base are used as raw materials, and the use of strong corrosive FSO is avoided3H is taken as a raw material; the process is simple, the continuous operability is strong, the product is easy to separate and purify, high-purity (more than or equal to 99 percent) HFSI can be prepared by reduced pressure distillation, and the yield can reach more than 90 percent; no chloride ion participates in the whole reaction, and the product quality is stable.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1
9g of NH was added to a 500mL autoclave4F (ACS grade), 100g triethylamine and 210g acetonitrile. The reaction kettle is sealed and pumped to negative pressure of-0.1 MPa (gauge pressure). Slowly introducing SO under the condition of continuous stirring2F2The pressure from the gas to the reaction kettle is 0.3MPa, and the reaction is controlledAnd (3) continuously replenishing sulfuryl fluoride to 0.3MPa when the temperature is about 25 ℃, and when the reaction pressure is reduced to 0.2MPa, sequentially circulating until the pressure is slowly reduced or not reduced, which indicates that the sulfuryl fluoride does not participate in the reaction, basically finishing the reaction, carrying out the reaction for 20 hours totally, consuming 60g of sulfuryl fluoride, obtaining 370g of light yellow transparent solution, and having no solid residue. Acetonitrile and unreacted triethylamine are removed by rotary evaporation under the conditions of 80 ℃ and 0.08MPa (gauge pressure) to obtain 145g of dark yellow solution, then 30g of concentrated sulfuric acid (mass percent 98%) is added, the mixed solution is distilled under reduced pressure, 40.5g of HFSI product (purity 99.5%) is collected at 85 ℃/650Pa, colorless solution is cooled to white crystals (melting point is 17 ℃) by ice water, and the yield is 92.0%.
Example 2
9g of NH was added to a 500mL autoclave4F (ACS grade), 100g triethylamine and 210g acetonitrile. The reaction kettle is sealed and pumped to negative pressure of-0.1 MPa (gauge pressure). Slowly introducing SO under the condition of continuous stirring2F2The pressure of the reaction kettle is maintained at 0MPa by the gas, the reaction temperature is kept at 25-28 ℃, the reaction is carried out for 24h, and 72g of SO is consumed2F2385g of a pale yellow transparent solution was obtained, and no solid remained. Acetonitrile and unreacted triethylamine are removed by rotary evaporation under the conditions of 80 ℃ and-0.08 MPa (gauge pressure), 138g of dark yellow solution is obtained, 25g of concentrated sulfuric acid (mass percent 98%) is added, the mixed solution is distilled under reduced pressure, 36.8g of HFSI product (purity 99.2%) is collected at 85 ℃/650Pa, colorless solution is cooled to white crystals by ice water, and the yield is 83.6%.
Example 3
9g of NH was added to a 500mL autoclave4F (ACS grade), 100g triethylamine and 210g acetonitrile. The reaction kettle is sealed and pumped to negative pressure of-0.1 MPa (gauge pressure). Slowly introducing SO under the condition of continuous stirring2F2The pressure of gas to the reaction kettle is 0.6MPa, the reaction temperature is controlled to be about 25 ℃, sulfuryl fluoride is continuously supplemented to 0.6MPa when the reaction pressure is reduced to 0.2MPa, the steps are sequentially circulated until the pressure is reduced slowly or not reduced, the reaction is carried out for 14 hours, 75g of sulfuryl fluoride is consumed, 379g of light yellow transparent solution is obtained, and no solid residue exists. Rotary evaporating at 80 deg.C and-0.08 MPa (gauge pressure) to remove BNitrile and unreacted triethylamine to obtain 150g of dark yellow solution, then 30g of concentrated sulfuric acid (mass percent 98%) is added into the dark yellow solution, the mixed solution is distilled under reduced pressure, 41.3g of HFSI product (purity 99.3%) is collected at 85 ℃/650Pa, a colorless solution is cooled by ice water to form white crystals, and the yield is 93.8%.
Example 4
9g of NH was added to a 500mL autoclave4F (ACS grade), 100g triethylamine and 210g acetonitrile. The reactor was sealed and pumped to a negative pressure of-0.1 MPa (gauge pressure). Under the condition of continuous stirring, sulfuryl fluoride gas is slowly introduced until the pressure of the reactor is 0.6MPa, the reaction temperature is controlled at 60 ℃, when the reaction pressure is reduced to 0.2MPa, sulfuryl fluoride is continuously added to 0.6MPa, the reaction is sequentially circulated until the pressure is reduced slowly or not reduced, the reaction is carried out for 10 hours, 86g of sulfuryl fluoride is consumed, 394g of light yellow transparent solution is obtained, and no solid residue exists. Removing acetonitrile solvent of reaction liquid by rotary evaporation under the conditions of 80 ℃ and 0.08MPa (gauge pressure) to obtain 162g of dark yellow solution, then adding 50g of concentrated sulfuric acid (mass percent is 98 percent), carrying out reduced pressure distillation on the mixed solution, collecting 32.4g of HFSI product (purity is 99.1 percent) at 85 ℃/650Pa, cooling the colorless solution with ice water to obtain white crystals, and obtaining the yield of 73.6 percent.
Claims (2)
1. A preparation method of bis (fluorosulfonyl) imide is characterized by comprising the following steps: 9g of NH was added to a 500mL autoclave4F. 100g triethylamine and 210g acetonitrile; sealing the reaction kettle and pumping the reaction kettle to a gauge pressure of-0.1 MPa; slowly introducing SO under the condition of continuous stirring2F2The pressure of the gas to the reaction kettle is 0.3MPa, the reaction temperature is controlled to be 25 ℃, when the reaction pressure is reduced to 0.2MPa, sulfuryl fluoride is continuously added to 0.3MPa, the steps are sequentially circulated, the reaction is carried out for 20 hours, 60g of sulfuryl fluoride is consumed, 370g of light yellow transparent solution is obtained, and no solid residue exists; removing acetonitrile and unreacted triethylamine by rotary evaporation at the temperature of 80 ℃ and the gauge pressure of-0.08 MPa to obtain 145g of dark yellow solution, then adding 30g of concentrated sulfuric acid with the mass percent of 98%, carrying out reduced pressure distillation on the mixed solution, and collecting 40.5g of HFSI product at the temperature of 85 ℃/650 Pa.
2. A preparation method of bis (fluorosulfonyl) imide is characterized by comprising the following steps: 9g of NH was added to a 500mL autoclave4F. 100g triethylamine and 210g acetonitrile; sealing the reaction kettle and pumping the reaction kettle to a gauge pressure of-0.1 MPa; slowly introducing SO under the condition of continuous stirring2F2The pressure of the gas to the reaction kettle is 0.6MPa, the reaction temperature is controlled to be about 25 ℃, sulfuryl fluoride is continuously supplemented to 0.6MPa when the reaction pressure is reduced to 0.2MPa, the steps are sequentially circulated, the reaction is carried out for 14 hours, 75g of sulfuryl fluoride is consumed, 379g of light yellow transparent solution is obtained, and no solid residue exists; removing acetonitrile and unreacted triethylamine by rotary evaporation at the temperature of 80 ℃ and the gauge pressure of-0.08 MPa to obtain 150g of dark yellow solution, then adding 30g of concentrated sulfuric acid with the mass percent of 98%, carrying out reduced pressure distillation on the mixed solution, and collecting 41.3g of HFSI product at the temperature of 85 ℃/650 Pa.
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| CN108975292A (en) * | 2018-09-17 | 2018-12-11 | 九江天赐高新材料有限公司 | A kind of preparation method of double fluorine sulfonyl imide compounds |
| CN109928372A (en) * | 2019-04-12 | 2019-06-25 | 广州理文科技有限公司 | A kind of preparation method of double fluorine sulfimides |
| US11591218B2 (en) | 2019-12-17 | 2023-02-28 | Honeywell International Inc. | Integrated processes for producing bis(fluorosulfonyl) imide |
| CN111320151A (en) * | 2020-02-18 | 2020-06-23 | 白银科奥夫化学科技有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| WO2021082450A1 (en) * | 2020-06-05 | 2021-05-06 | 广州理文科技有限公司 | Supercritical purification method for bis(fluorosulfonyl)imide |
| CN111717901B (en) * | 2020-06-23 | 2022-03-22 | 广州理文科技有限公司 | Method for preparing bis (fluorosulfonyl) imide by using anhydride-water system |
| US11772967B2 (en) | 2021-01-07 | 2023-10-03 | Honeywell International Inc. | Integrated processes for treatment of an ammonium fluorosulfate byproduct of the production of bis (fluorosulfonyl) imide |
| CN112897488B (en) * | 2021-03-19 | 2023-10-24 | 常州高优纳米新材料有限公司 | Method for preparing difluoro sulfimide by micro-channel reactor |
| CN112919435A (en) * | 2021-03-23 | 2021-06-08 | 常州高优纳米新材料有限公司 | Preparation method of high-purity bis (fluorosulfonyl) imide and alkali metal salt thereof |
| WO2024061955A1 (en) * | 2022-09-22 | 2024-03-28 | Specialty Operations France | Method for manufacturing bis(halogeno sulfonyl)imide |
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